JP2002533486A - Aqueous copolymer dispersion, production method thereof and use thereof - Google Patents

Abstract

  (57) [Summary] The present invention relates to aqueous copolymer dispersions. The aqueous copolymer dispersion is A) an aqueous dispersion of a copolymer having a solid content of 20 to 65% by weight, wherein the copolymer is composed of different types of monomers, and the weight content of the different types of monomers is only the above-mentioned monomers. An aqueous dispersion of the copolymer, selected within said predetermined limits such that the glass transition temperature of the synthetic resin consisting of -50 to + 35 ° C., and B) 0 to 10% by weight with respect to said copolymer A Benzophenone, acetophenone, one or more acetophenone derivatives or benzophenone derivatives without ethylenically unsaturated groups, or mixtures thereof; C) 0.3 to 10% by weight, based on the copolymer A, of an emulsifier; From 0 to 5% by weight, based on copolymer A, of protective colloid. Further, the present invention relates to a method for producing the above-mentioned dispersion and its use.

Description

DETAILED DESCRIPTION OF THE INVENTION

The present invention relates to novel aqueous copolymer dispersions, a process for their preparation and their use, especially in elastic coatings.

[0002] EP-A-0 458 144 describes that the synthetic resin comprises not only monomers such as acrylates, methacrylates, styrenes and vinyl esters, monoethylenically unsaturated acetophenone derivatives and / or benzophenone derivatives, but also at least Disclosed is an aqueous synthetic resin dispersion containing one type of unsaturated ketone or at least one type of aldehyde in a copolymerized form and also containing a compound containing at least two acid hydrazide groups and obtained by free radical emulsion polymerization. Have been. It is recommended that these synthetic resin dispersions be used for coating, bonding, sealing and impregnation.

[0003] The use of relatively expensive monoethylenically unsaturated acetophenone and / or benzophenone derivatives and compounds containing unsaturated ketone and / or aldehyde derivatives and at least two acid hydrazide groups which are added later The use of means that the corresponding synthetic resin is itself relatively expensive. The drawback of these synthetic resins is that, despite the high elongation at break, these films are stretched by a specified distance and resilience when a specified elongation is produced, or by a specified distance, and accordingly, Is that the resilience when left extended is not sufficient. A further disadvantage of coatings comprising these synthetic resins is often their poor stability when exposed to water for a short time after application to the substrate and their high water absorption. Further, these coatings are often prone to re-emulsification and / or blistering after brief exposure to water vapor.

[0004] EP-A-0599676 describes that the synthetic resin contains not only monomers such as acrylates or methacrylates and styrene, but also monoethylenically unsaturated acetophenone derivatives and / or benzophenone derivatives. Aqueous polymer dispersions having reactive dicyclopentadienyl groups are disclosed. These synthetic resin dispersions are recommended for use in elastic coatings.

[0005] Disadvantages of these binders are that the crosslinking process of the paint films of these binders proceeds relatively slowly, and that the paint lacks elasticity in terms of resilience after subjecting the paint to crack-induced elongation. That is enough. In addition, such synthetic resin-based coatings can have significant differences in properties when applied to the sun-facing side of a building or when applied to non-sunlit areas. Furthermore, during the preparation of synthetic resin dispersions by free-radical polymerization, the allylic double bonds have an inhibitory effect and thus hinder the preparation of these dispersions.

[0006] EP-A-0 778 296 describes that the synthetic resin contains not only monomers such as acrylates or methacrylates but also methylstyrene or other alkyl-substituted styrenes and, if necessary, acrylonitrile in copolymerized form. The present invention relates to an aqueous polymer dispersion. These synthetic resin dispersions are recommended as binders for elastic coatings and sealing compounds.

The disadvantages of these binders are that the process of crosslinking the paint films of these binders is relatively slow under the influence of light and that the resilience in terms of resilience after crack-induced elongation of the paint is not sufficient. That is. In addition, there may be significant differences in the properties of such synthetic resin-based coatings depending on whether the coating is applied to the sun-facing side of the building or to areas not exposed to the sun. A further disadvantage of coatings with these synthetic resins is that, in many cases, their stability after short application to water after application to the substrate is poor. Further, in many cases, these coatings are prone to re-emulsification and / or blistering after brief exposure to water vapor. In addition, the use of acrylonitrile in these binders both hydrolyzes the acrylonitrile groups in the copolymer, which tends to yellow the coating on basic substrates and poor stability of the coating, thereby reducing water sensitivity. Greatly increase.

Accordingly, an object of the present invention is that when coated, it has low water absorption, especially low re-emulsifiability after steam treatment, and good elongation at break and good relaxation after specified elongation. Is to develop a synthetic resin.

The object is to provide A) an aqueous copolymer dispersion having a solids content of 20 to 65% by weight,
The copolymer comprises: a) an α, β-monoethylenically unsaturated carboxylic acid having 3 to 6 carbon atoms and 1 to 1 carbon atoms.
40 to 99.9% by weight, preferably 65 to 85% by weight, of at least one ester with an alkanol of 8 and 0 to 40% by weight, preferably 15 to 35% by weight, of at least one vinyl aromatic compound (monomer a) B) 0.05 to 10% by weight of at least one α, β-monoethylenically unsaturated monobasic acid or dibasic acid having 3 to 8 carbon atoms and / or an anhydride thereof, and 3 to 8 carbon atoms. Wherein the nitrogen is at least one α, β-monoethylenically unsaturated carboxamide which may be mono- or di-substituted by an alkyl ether sulfate, alkyl sulfate, alkanol or alkyl having 5 or less carbon atoms. 1
0% by weight (monomer b), c) 0.05 to 10% by weight of at least one monoethylenically unsaturated cross-linking monomer (monomer c), and d) at least one other copolymerizable monoethylenically unsaturated monomer. And 0 to 30% by weight (monomer d) are in a copolymerized form, and the weight ratio of the monomers a, b, c and d is -50 to 35 ° C. Preferably -40 to 10 ° C, particularly preferably -30
An aqueous copolymer dispersion, which is selected within said predetermined range so as to have a glass transition temperature in the range of -10 ° C; and B) one or more benzophenones, acetophenones, or no ethylenically unsaturated groups 0 to 10% by weight, preferably 0.02 to 2% by weight, based on the copolymer A, of an acetophenone derivative or a benzophenone derivative, and C) 0.3 to 10% by weight, based on the copolymer A. D) 0 to 5% by weight, preferably 0.0% by weight of the protective colloid based on the copolymer A
5-5% by weight of an aqueous copolymer dispersion consisting essentially of:

The above α, β-monoethylenically unsaturated carboxylic acid having 3 to 6 carbon atoms and 1 to 1 carbon atoms
The compound used as an ester with the alkanol of No. 8 is preferably an ester of acrylic acid and / or methacrylic acid. Of these, methanol ester, ethanol ester, propanol ester, butanol ester, pentanol ester, 2-ethylhexanol ester, isooctanol ester, n-decanol ester and n-dodecanol ester are particularly important. Preferred vinyl aromatic compounds are styrene, methyl styrene, ethyl styrene, dimethyl styrene, diethyl styrene and trimethyl styrene, particularly preferably styrene.

The compounds used as α, β-monoethylenically unsaturated mono- or dibasic acids having 3 to 8 carbon atoms are preferably α, β-monoethylenically unsaturated carboxylic acids and water-soluble derivatives thereof. In particular, acrylic acid, methacrylic acid, ethacrylic acid, itaconic acid, fumaric acid and maleic acid and their anhydrides are particularly preferred. Furthermore, amides and monoamides of these acids are also suitable, of which acrylamide and methacrylamide, and also N-substituted derivatives thereof, such as N,
(N'-di) methyl (meth) acrylamide, N, (N'-di) ethyl (meth)
Acrylamide and N, (N'-di) isopropyl (meth) acrylamide are also preferred. Methacrylamide is particularly preferred. An acrylamide derivative in which nitrogen is mono- or di-substituted by an alkyl radical, alkanol radical, alkyl sulfate radical or alkyl ether sulfate radical having 5 or less carbon atoms may also be present. Furthermore, vinyl sulfonic acid, vinyl phosphonic acid, acrylamide glycolic acid and methacrylamide glycolic acid are very suitable. These synthetic resins preferably contain from 0.3 to 5% by weight of monomer b in copolymerized form. As the monomer b, a mixture of acrylic acid and methacrylic acid, particularly a mixture of acrylic acid, methacrylic acid and methacrylamide is particularly preferred.

Preferred monomers c have the formula CH₂= CH-Si (OX)₃(Where X is a hydrogen source
A silane, an acyl group and / or an alkyl group having 3 or less carbon atoms)
is there. Vinyltrimethoxysilane, vinyltriethoxysilane and vinyltris
-2-methoxysilane is particularly preferred. Further preferred monomers c have the formula CH ₂ = CZ-COO-Y-Si (OX)₃ (Where Z is a hydrogen atom or a methyl group and
And / or an ethyl group, and Y is a group represented by the formula C_nH_2n(Where n = 2-6)
X is a hydrogen atom, an acyl group and / or an alkyl having 3 or less carbon atoms.
Silane represented by the following formula), and particularly preferably α-methacryloxy
Ropirtrimethoxysilane, and even glycidyl (meth) acrylate or
Other ethylenically unsaturated derivatives of glycidol, such as glycidyl vinyl ether
It is. Further, keto group-containing monomers such as acetoacetoxy-functional monomers
-For example, acetoacetoxyethyl methacrylate, acetoacetoxybutyl
Methacrylate, acrylamidomethylacetylacetone and vinylacetoacetate
Tate, polymerizable diacetone derivatives such as diacetone acrylamide and dia
Seton methacrylamide, as well as acrolein, can also be used. further
, Alkoxyvinylsilane, (meth) acryloyloxy-alkylsilane, (
(Meth) acryloyloxyalkyl-sulfonate, sulfate or phos
Fate, ethene sulfonate and polymerizable ethylene urea derivatives such as N
-([Beta]-(meth) acryloxyethyl) -N, N'-ethyleneurea and N-
(Β-acrylamidoethyl) -N, N′-ethyleneurea is the monomer c
Can be used.

The monomers d include acrylic or methacrylic esters of diols, for example hydroxyalkyl (meth) acrylates, especially hydroxyethyl acrylate or 1,4-butanediol monoacrylate, and also acrylic of tetrahydrofurfuryl alcohol. Preference is given to using acid esters or methacrylic esters, halogen-containing monomers such as vinyl chloride and vinylidene chloride, unsaturated hydrocarbons such as ethylene, propylene, isobutene, butadiene and isoprene, and lower vinyl ethers. Similarly, unsaturated nitrogen compounds such as N-vinylformamide, N-vinylpyrrolidone, tetrahydrofurfurylamine, acrylonitrile and methacrylonitrile, furthermore
Ureido monomers such as β-ureidoethyl acrylate, β-ureidoethyl vinyl ether, N-dimethylaminoethyl-N′-vinyl-N, N′-ethyleneurea and N-methylaminoethyl-N′-vinyl-N, N '-Ethyleneurea can be used as monomer d. Also suitable are monoesters of α, β-monoethylenically unsaturated dicarboxylic acids having 4 to 8 carbon atoms and alkanols having 5 to 20 carbon atoms.

The synthesis wherein the monomer components a, b, c and d are selected such that the synthetic resin consisting of only these monomers has a glass transition temperature of −40 to 10 ° C., especially −30 to −10 ° C. Resin A is particularly preferred. Fox (TG Fox, Bull. A.
m. Phys. Soc. (Ser. II) 1, 123 [1956]),
The glass transition temperature of the copolymer is better approximated by the following equation: ^{1 / Tg = X 1 / Tg} 1 + X 2 / Tg 2 + ····· X s / Tg s ( ^{wherein, X 1, X 2, ····} X s are monomers 1, 2, ... - a weight ratio of ^s, Tg ^1, Tg 2, ... Tg ^s the monomer 1,2, ..., or s of the glass transition temperature of the respective homopolymer (Kelvin) is The glass transition temperatures of the homopolymer consisting of monomer a and the homopolymer consisting of monomer b are substantially known and are described, for example, in J. Brandrup, EH Immer.
gut, Polymer Handbook, 1st ed. Wiley, New
York, 1966 and 2nd edition, J.M. Wiley, New York, 197
5.

[0015] Acetophenone, benzophenone, and also acetophenone derivatives or benzophenone derivatives containing no ethylenically unsaturated groups have been found to be suitable as component B. It is particularly preferred to use benzophenones and / or benzophenone derivatives without ethylenically unsaturated groups, mixtures of benzophenone which are liquid at room temperature with suitable auxiliary substances being particularly advantageous from a technical point of view. Such mixtures are known, inter alia, from EP-A-0209831.

The proportion of component B based on copolymer A preferably ranges from 0.05 to 5% by weight. Component B is carefully incorporated into the initial dispersion containing at least one synthetic resin A by stirring, preferably with heating. In this case, the incorporation of component B by copolymerization is avoided, so that only the surface is crosslinked under actinic radiation in a well formulated coating. On the other hand, the properties of the coating are obtained by internal crosslinking with monomer c. The incorporation of the unsaturated benzophenone derivative by copolymerization results in a more uniform distribution of the benzophenone functionality, but at the same time, a loss of elasticity after prolonged irradiation with actinic radiation. This is because subsequently, internal crosslinking occurs in the film.

It is preferable to use a nonionic emulsifier and / or an ionic emulsifier as the emulsifier C.

Nonionic emulsifiers that can be used include, for example, alkyl polyglycol ethers, such as ethoxylated lauryl alcohol, oleyl alcohol or stearyl alcohol, or ethoxylated mixtures of coconut fatty alcohols; alkylphenol polyglycol ether; For example, octylphenol,
Nonylphenol, diisopropylphenol, triisopropylphenol,
Ethoxylated di-t-butylphenol or tri-t-butylphenol; or ethoxylated polypropylene oxide.

Suitable ionic emulsifiers are preferably anionic emulsifiers. These include alkali metal salts or ammonium salts of alkyl sulfonates, aryl sulfonates or alkyl aryl sulfonates, alkali metal salts or ammonium salts of alkyl sulfates, aryl sulfates or alkyl aryl sulfates, alkyl phosphates, aryl phosphates and aryl aryl phosphates. It can be an alkali metal or ammonium salt, or an alkali metal or ammonium salt of an alkyl phosphonate, aryl phosphonate or alkylaryl phosphonate, or a compound having another anionic end group. Further, an oligoethylene oxide unit or a polyethylene oxide unit may be present between the hydrocarbon radical and the anionic group. Typical examples include sodium lauryl sulfate, sodium undecyl glycol ether sulfate, sodium lauryl diglycol sulfate, sodium tetradecyl triglycol sulfate, sodium octyl phenol glycol ether sulfate, sodium dodecyl benzene There are sulfonates, sodium lauryl diglycol sulfate and ammonium tri-t-butylphenol penta- or octaglycol sulfate.

The compound used as the protective colloid D preferably has a degree of substitution (the degree of substitution is
(The average number of carboxymethyl groups introduced per anhydroglucose unit) 0.4 to 2.9, preferably 0.4 to 1.5, particularly preferably 0.1 to 0.4.
6 to 1.4, the 2% strength aqueous solution having a B-type viscosity at 25 ° C. (20 rpm) of less than 2000 mPa (spindle 3), preferably less than 500 mPa (spindle 2) and particularly preferably less than 100 mPa (spindle 1). ) Is a water-soluble carboxymethyl cellulose. The carboxymethyl cellulose is preferably used in the form of its ammonium salt or alkali metal salt. Suitable commercial products include, for example, Blanose 7M® from Clariant,
Blanose 7UL (registered trademark) and Blanose 7EL (registered trademark)
As well as Ambergum 3021® from Aqualon.
The carboxymethyl cellulose of the present invention may optionally contain a substituent, particularly an alkyl or hydroxyalkyl radical having 1 to 4 carbon atoms, an alkyloxyalkyl radical having 2 to 6 carbon atoms, or a dialkylamino radical having a total of 2 to 6 carbon atoms. Further, it may be included. Particularly suitable compounds include, for example, methylcarboxymethylcellulose, ethylcarboxymethylcellulose, hydroxyethylcarboxymethylcellulose, hydroxypropylcarboxymethylcellulose, methoxyethylcarboxymethylcellulose, ethoxyethylcarboxymethylcellulose and diethylaminocarboxymethylcellulose. Further examples of protective colloids that can be used include high molecular weight compounds such as polyvinyl alcohol, polyvinylpyrrolidone, polyacrylamide, polymethacrylamide, polycarboxylic acids or their alkyl metal salts and / or ammonium salts.

The polymer used as the synthetic resin A can be prepared by known methods, that is, free radical bulk polymerization, free radical solution polymerization, free radical suspension polymerization, and free radical emulsion polymerization. However, a preferred preparation state of the aqueous synthetic resin composition of the present invention is an aqueous form, and therefore, it is also preferable to use the synthetic resin A in this form. Thus, the resin is prepared in an aqueous medium, under the known conditions of free-radical emulsion polymerization, in the presence of a water-soluble free-radical initiator and an emulsifier C, and, if necessary, protective colloid D, regulators and / or further auxiliaries. Is preferably prepared by polymerizing each monomer in the presence of The polymerization is carried out according to a conventional method of emulsion polymerization, by emulsifying the monomer in an aqueous phase in the presence of an emulsifier, an initiator and a protective colloid,
It is carried out by polymerizing them at a temperature of 60-95 ° C. The emulsion polymerization can be carried out according to a conventional method known to those skilled in the art, such as a batch method, a monomer measuring method, or an emulsification supply method. After the initial polymerization of a small amount of the monomer, the operation is preferably performed according to an emulsification supply method in which the remaining amount of the monomer is metered in as an aqueous emulsion. If necessary, an emulsion of a plurality of different monomers can be metered in sequentially. Like the emulsifier, the protective colloid can be partly included in the initial charge to the reactor and / or metered in with the monomer emulsion.

The preparation of the high-quality dispersions according to the invention is based on the application of knowledge in the field of emulsion polymerization (even though knowledge is not described here). Therefore, important properties (for example, the water resistance of the dispersion film) may be adversely affected unless the usual methods known to those skilled in emulsion polymerization are followed. Thus, based on the amount of polymer, the dispersion is substantially free of ionic emulsifiers, preferably up to 3% by weight, particularly preferably up to 2% by weight, and / or preferably up to 2% by weight of nonionic emulsifiers. Should be less than 6% by weight, particularly preferably less than 4% by weight. In particular, it is preferable to use only the ionic emulsifier at 2% by weight or less.

To initiate and carry out the polymerization, use is made of oil-soluble and / or preferably water-soluble free-radical initiators or redox systems. Preferred examples include hydrogen peroxide, potadium peroxodisulfate, sodium peroxodisulfate, ammonium peroxodisulfate, dibenzoyl peroxide, lauryl peroxide, tri-t-butyl peroxide, bisazodiisobutyronitrile. Yes,
These may be used alone or in reducing components such as sodium bisulfite, Rongal
For use with it®, glucose, ascorbic acid, and other compounds with reducing action. Peroxodisulfate is particularly preferably used.

In the emulsion polymerization, the temperature is generally 30 to 90 ° C., preferably 50 to 90 ° C.
And the polymerization initiator is typically used in an amount of 0.1 to 10% by weight based on the total amount of monomers.

In addition, regulators such as mercaptans, especially n-dodecyl mercaptan, thiophenol and 2-methyl-5-tert-butylthiophenol can be used. The modifier is typically used in an amount of 0 to 1% by weight, preferably 0 to 0.5% by weight, and it is particularly preferred to prepare the dispersion with less than 0.3% by weight of the modifier.

The dispersion is prepared using an aqueous ammonia solution, an aqueous alkali metal hydroxide solution and an aqueous alkaline earth metal hydroxide solution, typically at a pH of 6.5 to 10, preferably 7.0.
Adjust to ~ 9.0.

If desired, the dispersion may be a film-forming auxiliary such as white spirit, Te.
xanol®, butyl diglycol and butyl dipropylene glycol, plasticizers such as dimethyl phthalate and dibutyl phthalate, dispersants such as polyacrylic acid and the corresponding copolymers such as Lopon 890® and Dispex G40. ®, polyacrylate or polyurethane based thickeners, such as Borchigel L75® and Tafigel PUR40®, preservatives, defoamers such as mineral oil or silicone defoamers, Wetting agents such as aminomethylpropanol and other additives typically used in preparing coating compositions can be included.

The synthetic resin formulations according to the invention are particularly suitable for use as coating compositions for walls, floors and ceilings, as elastic binders for leather fibers, as marking paints for roads and highways, and also for primers, In these applications, it ensures durability bridging of cracks, low tack, low fouling and good water resistance.

The present invention will be described in more detail with reference to the following examples, but the present invention is not limited thereto.

[0030] Example 1 Preparation n- butyl acrylate 50g of aqueous copolymer dispersions, and ethylhexyl acrylate 20g, styrene 27 g, and methacrylic acid 2g, and vinyltrimethoxysilane 1 _{g, C 1 2} - alkyl triethylene glycol ether sulfate The monomer mixture with 1.8 g of the Na salt is emulsified in 100 g of water.

Subsequently, 10% of an aqueous solution prepared by adding 10 g of water to 0.5 g of sodium peroxodisulfate was added to 10% of the aqueous emulsion, and the mixture was stirred at a temperature of 80 ° C. Heat to Subsequently, the remaining amount of the aqueous emulsion and, in parallel with it, over a period of 2 hours, except for 2.5 hours, the remaining amount of the aqueous initiator solution are continuously supplied with stirring. The polymerization temperature is 80 ° C.

When the metered addition of the initiator has ended, the polymerization is continued for a further hour.

0.7 g of benzophenone is added with stirring to the obtained about 50% aqueous synthetic resin dispersion.

Example 2 (comparative) Preparation of aqueous copolymer dispersion 50 g of n-butyl acrylate, 20 g of 2-ethylhexyl acrylate, 27 g of styrene, 2 g of methacrylic acid and Na salt of C ₁₂ -alkyltriglycol ether sulfate A monomer mixture with 1.8 g (without vinyltrimethoxysilane) is emulsified in 100 g of water.

Subsequently, 10% of an aqueous solution prepared by adding 0.5 g of sodium peroxodisulfate to 10 g of water was added to 10% of the aqueous emulsion, and the mixture was stirred at a temperature of 80 ° C. Heat to Subsequently, the remaining amount of the aqueous emulsion and, in parallel with it, over a period of 2 hours, except for 2.5 hours, the remaining amount of the aqueous initiator solution are continuously supplied with stirring. The polymerization temperature is 80 ° C.

When the metered addition of the initiator has ended, the polymerization is continued for a further hour.

[0037] 0.7 g of benzophenone is added with stirring to the obtained about 50% aqueous synthetic resin dispersion.

Example 3 Demonstration of Increased Elasticity and Resilience and Reduced Surface Tack and Slightly Reduced Elongation at Break of a Plastic Formulation of the Invention After UV Irradiation Two plastic dispersions, ie, Example 1 Synthetic resin dispersion and Example 2 (Comparative Example)
Was made into a film having a dry thickness of 0.5 mm over 7 days under standard conditions. The membrane is then touched by hand to test the surface tack and evaluated according to DIN 53230 (0 = best score, 5 = worst score). A.Zo
sel, `` Research on the Properties of cured films of aqueous dispersions
storage elastic modulus (G '[N / mm ² ]; using according to the properties of cured films of aqueous dispersions of polymers) in Double Liaison Chimie des Peintures-284, October 1987; (50 ° C; 0.1 Hz). In a further experiment, the film is subjected to UV irradiation for 0.5 hours and the surface tack and storage modulus are measured again. The results are as shown in Table 1. In order to measure the elongation at break of the dispersion film, a film having a size of 0.8 × 3 × 20 mm was placed on an Inst
Examine with a RON Series IX Materials Testing System and measure and record both elongation at break and stress at break of the film. To measure the resilience of these films, a film of dimensions 0.8 × 3 × 20 mm is fixed vertically to a stand and a 200 g weight is fixed to the lower edge of the film. After 24 hours, the elongation (unit:%) of the film is measured, and the weight is removed. After a further 24 hours without weight (relaxation), the residual elongation (unit:%) of the film is measured. These results are as shown in Table 2.

Table 1 G 'tan δ = surface tack tack G "/ G' (according to DIN53230) (scale division) Example 1 Before UV irradiation 3.63 0.19 3950 After UV irradiation 4.21 0.16 1 320 Examples 2 Before UV irradiation 1.59 0.48 51450 After UV irradiation 1.85 0.39 4 1050

Table 2 Elongation at Break Load Elongation Under Load Residual Elongation After Loading (%) [MPa] (%) (%) Example 1 Before UV Irradiation 792 3.21 280 15 After UV Irradiation 675 3.45 225 10 Example 2 Before UV irradiation 3945 0.40 Tear occurrence Tear occurrence After UV irradiation 797 0.87 Tear occurrence Tear occurrence

Example 4 Demonstration of increased water resistance, reduced blocking resistance and low reduction in elongation at break of UV coatings of elastic coatings using the binders of the invention External building paints of the following general composition Prepare according to the procedure. Binder: 41.0 g Water: 19.4 g Hydroxyethyl cellulose: 0.3 g Tetrasodium pyrophosphate (25% concentration solution): 0.1 g Chloroacetamide: 0.2 g White spirit: 0.7 g Ammonium salt of polyacrylic acid (40 % Solution): 0.3 g Silicone defoamer: 0.5 g Ammonia solution (25% concentration): 0.2 g Titanium dioxide (average particle size 1 μm): 13.0 g Talc (average particle size 5 μm): 5.0 g Carbonic acid Calcium (average particle size 2.5 μm): 10.0 g Calcium carbonate (average particle size 5 μm): 9.0 g 30% strength polyurethane thickener solution: 0.3 g

The dispersion prepared in Example 1 and the dispersion prepared in Example 2 (Comparative Example) are used as binder.

To measure the elongation at break of a paint film, a film formed using a 400 μm coating bar and having a dry dimension of 0.12 × 15 × 50 mm was
Before the QUV irradiation and 28 days after the QUV irradiation, the film is examined with an Instron series IX material test system (according to DIN 53455), the elongation at break of the film and the strain at the tear point of the film are measured and recorded.

In order to measure the resilience of these paint films, the resulting films (dimensions: 0.32 × 60 × 50 mm) were drawn down using a 1000 μm box-type coating bar and dried (standard conditions / 7 days). And fix an 800 g weight to the bottom edge of the film. After 24 hours, the elongation (unit:%) of the film is measured, and the weight is removed. After a further 24 hours without weight (relaxation), the residual elongation (unit:%) of the film is measured.

When measuring the blocking resistance, a dispersion film, a paint film or a varnish film is pressed against each other at room temperature by applying a predetermined force [2 kg]. Subsequently, the force [g] required to separate a given area (6.25 cm ² ) of the film from each other
Is measured again. The smaller the force per film area required to separate the films from each other, the better the blocking resistance. Thus, blocking resistance is a measure of the surface tack between films.

The first water absorption was determined by immersing a dried paint film drawn down with an 800 μm coating bar in water and measuring the weight gain after drying under standard climatic conditions for 7 days.
It is determined by recording in% of the initial weight. After drying and further immersion in water, the second water absorption is measured. The second water absorption is usually low. This is because some of the emulsifier is washed out of the film and therefore represents an aged film for the conditions of use.

To measure the initial water resistance, a stripe (approximate dimensions: 30 cm long × 6 cm wide) of the external architectural paint was applied to a box-type coating bar (gap height: 30).
(0 μm) on a Leneta film and the film is dried for 2 hours in a climate controlled chamber (standard climatic conditions). Petri dish (9.5c diameter)
Calibrate the photometer to 100% using 50 g of deionized water in m).
From the drawdown paint film stored in the climate control chamber for 2 hours,
Cut a film strip (dimensions: 6 cm x 26 cm). The strip is placed around the wall of a 400 ml glass beaker (broad form) with the coating side facing inward. Weigh 10 g of plastic granules and 300 g of deionized water in a glass beaker. On a magnetic stirrer, the contents of the beaker are stirred at about 750 rpm using a magnetic stir bar such that the granules hit the coated surface of the film. After 1 hour, 2 hours and 3 hours of stirring, the turbidity of the wash water is measured. For this purpose, 50 g of wash water is taken out each time, weighed in a Petri dish and placed in a calibrated photometer to measure turbidity. After the measurement, the solution is returned to the glass beaker. After 3 hours, the film is visually inspected for any changes.

To measure the blistering behavior of the paint, the paint is applied using a decorating roller so as to sufficiently cover the front of the fiber cement slab. After drying for 24 hours, a second coat is applied in a similar manner. Carefully apply multiple samples to one fiber cement slab. After drying the second coat for 24 hours, the fiber cement slab is placed in a water bath (blister bath) with the application side facing down. Water bath temperature is 5
At 0 ° C., the distance from the sample slab to the water surface is 15 cm, and the sample slab completely covers the water bath. After 8 hours of exposure, the sample slab is removed from the blister bath, set up vertically and dried at room temperature. Drying time should be at least 2 hours. The dried sample is evaluated visually. The evaluation is based on bleaching, spotting and whitening according to the rating system (1 = very good, no whitening or spotting; 5 = poor, severe spotting and / or whitening).

The results obtained by the above-described measurement method are as shown in Table 3.

Table 3 Example 1 Example 2 Elongation at break [%] 350 640 Stress [MPa] 4.1 2.2 Elongation at break after UV irradiation [%] 285 310 Stress after UV irradiation [MPa] 4.3 2.3. 3 Elongation under load [%] 70 Tear generation Residual elongation after load [%] 10 Tear generation Blocking resistance [g / 6.25 cm ² ] 160 1000 First water absorption [%] 7 10 Second water absorption [%] 6 8 Blister test 2 2 Initial water resistance 1 2

Example 5 Demonstration of Increased Shear Stability of a Dispersion of the Invention in the Presence of a Filler 50 g of n-butyl acrylate, 20 g of 2-ethylhexyl acrylate, 27 g of styrene, 2 g of methacrylic acid and vinyltrimethoxy 1 g of silane,
A monomer mixture of 0.3 g of Aquargum Ambergum 3021® and 1.8 g of Na salt of C ₁₂ -alkyltriglycol ether sulfate is emulsified in 100 g of water.

Subsequently, 10% of an aqueous solution prepared by adding 0.5 g of sodium peroxodisulfate to 10 g of water was added to 10% of the aqueous emulsion, and the mixture was stirred at a temperature of 80 ° C. Heat to Subsequently, the remaining amount of the aqueous emulsion and, in parallel with it, over a period of 2 hours, except for 2.5 hours, the remaining amount of the aqueous initiator solution are continuously supplied with stirring. The polymerization temperature is 80 ° C. When the metered addition of the initiator has ended, the polymerization is continued for a further hour. This dispersion together with the dispersion prepared in Example 1 is investigated for shear stability. The solids content of the two dispersions is adjusted to exactly 45% with deionized water, and 100 g of a 45% solids dispersion
Is mixed with 200 g of coarse calcium carbonate (average particle size: 23 μm) with a glass rod in a 500 ml beaker. Next, this mixture is mixed in a dissolver (disc diameter: 5 cm) under the conditions of 1000 rotations and 1 minute. Next, the dissolving machine was stopped and 3000 rpm
Restart at a rotation speed of m and simultaneously start the stopwatch. The mixture
Stir under these conditions until loss of stability (aggregation, formation of coarse particles) can be visually confirmed. The time between starting the stirrer (3000 rpm) and the loss of stability of the mixture is recorded as a measure of stability. The results are as shown in Table 4.

Table 4 Example 1 Example 5 Shear Stability When Filler Used [min] 6.5 16.5

[Procedural Amendment] Submission of translation of Article 34 Amendment

[Submission date] February 7, 2001 (2001.2.7)

[Procedure amendment 1]

[Document name to be amended] Statement

[Correction target item name] Claims

[Correction method] Change

[Contents of correction]

[Claims]

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁷ Identification symbol FI Theme coat ゛ (Reference) C09D 157/10 C09D 157/10 163/00 163/00 183/04 183/04 (72) Inventor Rolf, Kloppka Zelzen, Federal Republic of Germany, Röhler-Kraft-Strase, 17 (72) Inventor Susana, Maria, De, Almeida, Cal Barho Portugal Oeiras, Lua, Porto, Alegre, 13, 5, Esquina F-term (reference) 4J002 AB032 BE022 BG002 BG041 BG051 BG132 BJ002 ED037 EE036 EV257 EW047 FD146 FD202 FD317 GH00 GJ01 GJ02 4J038 BA092 CC021 CG141 CH031 CH041 DB221 GA07 GA09 GA15 HA156 JA33 KA09 LA02 MA08 MA10 MA13 PB05

Claims (14)

[Claims] 1. A) An aqueous copolymer dispersion having a solids content of 20 to 65% by weight, said copolymer comprising: a) an α, β-monoethylenically unsaturated carboxylic acid having 3 to 6 carbon atoms and 1 carbon atom. ~ 1
40 to 99.9% by weight of at least one ester with an alkanol of 8 and 0 to 40% by weight of at least one vinyl aromatic compound (monomer a); b) at least one α, β-C 3-8 carbon atom; Monoethylenically unsaturated monobasic acid or dibasic acid and / or anhydride thereof in an amount of 0.05 to 10% by weight, and an alkyl ether sulfate having 3 to 8 carbon atoms and having 5 or less carbon atoms, At least one α, β-monoethylenically unsaturated carboxamide, which may be mono- or di-substituted by sulfate, alkanol or alkyl;
0% by weight (monomer b), c) 0.05 to 10% by weight of at least one monoethylenically unsaturated cross-linking monomer (monomer c), and d) at least one other copolymerizable monoethylenically unsaturated monomer. 0 to 30% by weight (monomer d) and in a copolymerized form, wherein the weight ratio of the monomers a, b, c and d is such that the synthetic resin comprising only these monomers has a temperature of -50 to 35 ° C. An aqueous copolymer dispersion selected within said predetermined range to have a glass transition temperature in the range; B) benzophenone, acetophenone, one or more acetophenone derivatives or benzophenones without ethylenically unsaturated groups 0 to 10% by weight, based on the copolymer A, of a derivative or a mixture thereof; and C) 0.3 to 10% by weight of the emulsifier based on the copolymer A. The amount% and, D) an aqueous copolymer dispersion consisting essentially of a protective colloid from a 0-5% by weight the copolymer A reference. 2. An α, β-monoethylenically unsaturated carboxylic acid having 3 to 6 carbon atoms and 1 to 1 carbon atoms.
The aqueous copolymer dispersion according to claim 1, wherein the ester of alkanol 8 is an ester of acrylic acid and / or methacrylic acid. 3. The aqueous copolymer dispersion of claim 1, wherein said vinyl aromatic compound is styrene. 4. The α, β-monoethylenically unsaturated monobasic acid or dibasic acid having 3 to 8 carbon atoms is an α, β-monoethylenically unsaturated carboxylic acid or a water-soluble derivative thereof. An aqueous copolymer dispersion according to claim 1. 5. The aqueous copolymer dispersion of claim 1, wherein said α, β-monoethylenically unsaturated carboxamide is methacrylamide. 6. The monomer c has the formula CH ₂ ＣＨCH—Si (OX) ₃ , wherein X is a hydrogen atom,
The aqueous copolymer dispersion according to claim 1, which is a silane represented by an acyl group and / or an alkyl group having 3 or less carbon atoms. 7. The method according to claim 1, wherein the monomer c has the formula CH ₂ ＣCZ—COO—Y—Si (OX) ₃ , wherein Z is
Is a hydrogen atom or a methyl group and / or an ethyl group, Y is a group represented by the formula C _n H _2n (where n = 2 to 6), and X is a hydrogen atom, an acyl group and / or Or an alkyl group having 3 or less carbon atoms). 8. The aqueous copolymer dispersion of claim 1, wherein said monomer c is glycidyl (meth) acrylate. 9. The composition according to claim 1, wherein the weight proportions of the monomers a, b, c and d are such that the synthetic resin consisting of these monomers alone has a glass transition temperature of -40 to 10 ° C. An aqueous copolymer dispersion according to at least one of the preceding claims. 10. The aqueous copolymer dispersion according to at least one of the preceding claims, wherein component B is a benzophenone and / or a benzophenone derivative free of ethylenically unsaturated groups. 11. The aqueous copolymer dispersion according to claim 1, wherein the emulsifier C is a nonionic and / or anionic emulsifier. 12. The aqueous copolymer dispersion according to claim 1, wherein the protective colloid D comprises a water-soluble carboxymethylcellulose having a degree of substitution of 0.4 to 2.9. 13. The process for preparing an aqueous copolymer dispersion according to claim 1, wherein the monomers a, b,
subjecting c and d to free radical emulsion polymerization in an aqueous medium in the presence of a water-soluble free-radical initiator, an emulsifier C and optionally a protective colloid D, a regulator and / or further auxiliaries. Manufacturing method. 14. Use of the aqueous copolymer dispersion according to at least one of claims 1 to 12 in wall, floor and ceiling coating compositions, road and highway marking paints and primers.